Method of rendering an ink strippable

ABSTRACT

A method of rendering an ink, selected from the group consisting of an oil-modified alkyd ink and a drying oil ink, strippable from a surface, upon which it is applied and dried, is disclosed. The method comprises applying to the printed ink, prior to the drying thereof, a modifying powder comprising a petroleum resin.

This is a division of application Ser. No. 879,324 filed Feb. 21, 1978now U.S. Pat. No. 4,157,936.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a method of rendering an ink strippable andmore particularly, to rendering a pattern of an oil-modified alkyd inkor a drying oil vehicle ink strippable from a surface upon which it isapplied and dried.

2. Discussion of the Prior Art

A method for fabricating printed wiring boards involves the so-called"subtractive" technique. In the subtractive technique a laminatecomprising metal sheets or laminae, e.g., copper laminae, adherentlydeposited or held on opposed surfaces of a dielectric substrate isselected for treatment. At least one of the metal laminae is selectivelycoated with an etch resistant material to form a masking pattern. Theresultant masked surface is then subjected to an etchant whereby theunmasked portions of the metal layer are removed by etching. The maskingpattern is then removed to yield a conductive pattern remaining on thedielectric substrate.

In practice, the etch resistant material typically comprises aphotoresist which has to be initially selectively exposed to a source oflight energy, followed by solvent development to form the maskingpattern. Utilizing such a photoresist material is both time consumingand expensive. Alternatively, etch-resistant inks with solvent vehicleshave been utilized as masking materials. These inks are screen printedon the metal surface and then dried by heating the surface and drivingoff the solvents employed. The problems with using such materials arethat screen printing is a slower process than other printing techniques,such as offset printing, line widths under 20 mils are generally notfeasible and also pollution is involved whenever solvents have to bedriven off from an applied ink.

Offset printing techniques have been utilized to form the maskingpattern. However, difficulties are encountered in finding inks which areboth suitable for printing techniques, such as offset printing, andwhich can be easily or practically removed from the metal surface afterserving as an etch resist. Oftentimes the ink or resist pattern cannotbe easily removed, as by treatment with a solvent, and must be removedby such expedients as mechanical grinding. U.S. Pat. No. 2,602,731reveals such an expedient.

A group of inks which are suitable for offset printing comprises resinswhich are known as oil-modified alkyd resins. An oil-modified alkydresin comprises the reaction product of a dibasic (difunctional) acid oracid anhydride, e.g., phthalic anhydride, a polyol, e.g., glycerin, anda drying oil fatty acid, e.g., levulinic acid. Another group of inkswhich are suitable for offset printing comprises resins or vehiclesknown as drying oils. These inks are formulated and manufactured fromsuch typical oils as linseed, tung, soybean, safflower, dehydratedcastor, poppyseed, oiticia and perilla oils. Both groups of inks, upondrying, that is upon polymerizing and/or crosslinking, form a film whichresists scuffing and abrasion and because of this, find wide utility indecorating metal surfaces. However, these alkyd containing and dryingoil containing inks, upon drying, and nearly impossible to remove bysolvent stripping. Such alkyd resin and drying oil containing inks arenot therefore being used for offset printing etch resist patterns insubtractive fabrication of printed wiring boards.

A method of rendering an oil-modified alkyd resin ink pattern and adrying oil vehicle ink pattern capable of being readily solvent strippedfrom a surface to which it is applied is needed and is desired,especially for offset printing of resist patterns in subtractive printedwiring board manufacture.

SUMMARY OF THE INVENTION

This invention relates to a method of rendering an ink strippable andmore particularly, to rendering a pattern of an oil-modified alkyd inkor a drying oil vehicle ink strippable from a surface upon which it isapplied and dried. The method comprises applying to the ink, prior tothe drying thereof, a modifying powder comprising a petroleum resin.

DETAILED DESCRIPTION

The present invention will be discussed primarily in terms of solventstripping a dry offset printed ink pattern, comprising an oil-modifiedalkyd resin or a drying oil ink, from a metallic copper surface. It willbe readily appreciated that the inventive concept is equally applicableto stripping the drying oil or alkyd ink from other surfaces, metallicor non-metallic, which are chemically compatible with the ink and withthe solvent employed to strip the ink. It will also be appreciated thatthe ink may be printed either in a blanket fashion (not in a pattern) tocover the surface or in a pattern using any conventional printingtechnique such as lithography or wet offset, dry offset or letterset,letterpress and intaglio printing techniques, as well as brushing andstenciling techniques.

It has now been discovered that solvent-free printing inks comprising anoil-modified alkyd resin or a drying oil can be rendered solventstrippable from a surface upon which such inks are applied and dried.Thus, in accordance with the present invention, a solvent-free inkcomprising an oil modified alkyd resin or a drying oil is selected. Oilmodified alkyd resin containing inks are well known in the printing artas described in "PRINTING AND LITHO INKS," Herbert Jay Wolfe, SixthEdition, 1967, published by MacNair-Dorland Company, New York City.Typically an oil-modified alkyd resin is the reaction product of (1) amultifunctional acid or acid anhydride, (2) a multifunctional polyol and(3) a monofunctional (monobasic) drying oil fatty acid or monoglyceride.Some suitable multifunctional acids or anhydrides include ortho, meta,and para-phthalic acids and anhydrides, succinic, adipic and sebacicacids. Some suitable polyols include glycerine, neopentyl glycol,trimethylol-ethane and trimetholol-propane. Some suitable drying oilfatty acids include linoleic, licanic and eleostearic acids.

Drying oil or drying oil vehicle containing inks are also well known inthe printing art as also described in Printing and Litho Inks, HerbertJay Wolfe. Typically, these inks are manufactured from linseed, tung,soybean, safflower, dehydrated castor, poppyseed, oiticia and perillaoils.

Selected is a metal clad laminate of a dielectric base, e.g., a copperclad laminate of a thermosetting of thermoplastic resin base, the sheetor film of metal being bonded to it by heat and pressure in the mannerconventionally employed in preparing blank circuit boards for use insubtractive processing of printed circit boards. The laminate is thenoriented in an offset printing press, typically by locating pins of thepress entering indexing holes in the laminate. An oil-modified alkyd inkpattern or a drying oil ink pattern, corresponding to a desired circuitpattern, is then offset printed on a metal lamina or surface of thelaminate, to thereby delineate an uninked pattern comprising theuncoated metal portions. The uninked pattern is destined to be etchedand thereby removed from the laminate.

After the printed pattern is transferred to the metal surface, and whilethe ink is wet or tacky, i.e., has not polymerized or crosslinked to ahardened, non-flowing mass, a modifying powder is dusted or applied inany conventional manner to the inked surface. The modifying powderadheres only to the wet and tacky printed image and the excess thereofis removed, as for example by being blown away by a pressurized gas,removed by vacuum, or otherwise removed. The resultant powdered surfaceis then heated employing any conventional means and technique, e.g., useof heat lamps, ovens, etc., to fuse the modifying powder and the inkedpattern to the metal surface to form an etch resist pattern thereonwhich can be solvent stripped therefrom.

A suitable modifying powder is one which is resistant to the etchantdestined to be employed to etch metal portions of the laminate and whichis capable of rendering the oil-modified ink or drying oil ink patternsolvent strippable from the metal surface after it has been fused ordried thereupon. A suitable modifying powder comprises a petroleum resinwhich is a low molecular weight hydrocarbon resin, usually below 2000 inaverage molecular weight, typically having a softening point between100° and 120° C., which is made, not from one chemical, but from a blendof many. The petroleum resin is derived by the catalytic polymerizationof deeply cracked petroleum stocks. Petroleum resins, their propertiesand commercial availability, are described in Encyclopedia of ChemicalTechnology, Raymond E. Kirk and Donald F. Othmer, Editors, SecondEdition, Volume 11, at pages 248 through 250, published by IntersciencePublishers, New York, 1966. Suitable commercial petroleum resins whichare available are the "PICCOPALE" resins, such as for example "PICCOPALE100, 100 BHT, 100 SF and 100 HM" resins available from HerculesIncorporated, Wilmington, Delaware. Such resins are high softening pointmembers of a series of low molecular weight, aliphatic hydrocarbonresins derived mainly from a five carbon containing diolefin.

The amount of modifying powder employed should be sufficient to yield adried or fused resist pattern having a thickness of at least two timesthe original thickness of the wet or tacky ink pattern. Also, theresultant powdered surface should be heated at a temperature and for aperiod of time sufficient to fuse the modifying powder to form a powdercoat over the inked pattern. It is to be noted and stressed hereat thatthe modifying powder cannot be added to the oil-modified alkyd ink ordrying oil ink prior to the printing thereof. If such is done, then theresultant printed pattern cannot be readily solvent stripped from thesurface upon which it is applied and dried. The modifying powder must beapplied to the surface of the wet or tacky inked pattern and then heatedto form a coat thereover. It is hypothesized that the modifying powdercost acts as a mask which prevents the oil-modified alkyd ink or thedrying oil ink from adequately reacting with oxygen which results inextensive crosslinking and thus the inability to be solvent stripped.However, this is a hypothesis only and the invention disclosed herein isnot to be limited thereby. Exemplary, the powdered surface is heated ata temperature of 125° C. to 150° C. for 5 to 10 minutes when a modifyingpowder is employed having a softening point of 100° C. to 175° C.

After the powdered surface is heated to form the resist pattern, etchingthereof is then carried out in a conventional manner. Typically, forcopper metal, the resultant resist patterned laminate is treated, e.g.,by spraying, with a solution comprising ferric chloride, whereby theuninked or exposed metal pattern is etched and removed from thelaminate. The metal portions underlying the resist pattern are protectedfrom the etchant and thus are retained.

Typically, the etched laminate is rinsed in water, neutralized, e.g., insodium bicarbonate when FeCl₃ is the etchant, and again rinsed in water.The resultant laminate is then treated, as by immersion, with a suitablesolvent for the modifying powder coated inked pattern. A suitablesolvent is one which will dissolve or strip the dried, modifying powdercoated ink pattern from the surface to which it is applied withoutreacting with such a surface. Some typical suitable solvents includechlorinated hydrocarbons, such as methylene chloride, trichloroethane,trichloroethylene, etc.; and aromatic hydrocarbons such as toluene,xylene, etc. The laminate is treated with the solvent for a period oftime sufficient to remove or strip the fused powder coated, oil-modifiedalkyd ink pattern from the metal surface underlying it to yield aprinted circuit board having an uncoated or bared circuit patternthereon.

EXAMPLE I

For comparison purposes a 154.8 cm.² surface of a 0.0035 cm. thickcopper layer of a commercially obtained copper clad dielectric baselaminate was offset printed in a pattern with an ink comprising asoybean oil-modified isophthalic-pentaerythritol alkyd resin having anoil content of 50 to 60 percent by weight, a viscosity of 1100 to 1300poise at 77° F. and a maximum acid number of 15 (obtained from SuperiorVarnish and Drier Company and designated as "Soya Alkyd 3808"). Theprinted surface was then oven heated at 150° C. for 15 minutes to drythe inked pattern on the surface. The inked laminate was then passedthrough a conventional spray etcher using a copper metal etchant(commercially obtained and designated as "HUNT HI-SPEED CIRCUIT ETCH")at 85° F. to remove the uninked portions of the copper, therebydelineating an ink coated copper pattern on the dielectric of thelaminate. After 14 days, the resultant etched laminate was then immersedin an ultrasonically agitated solvent bath comprising hot 50° C.) methylchloroform. The inked pattern was not removed or stripped after oneminute in the solvent bath.

EXAMPLE II

The procedure of EXAMPLE I was repeated except that after the inkedpattern was printed on the surface, a modifying powder was applied bymeans of sprinkling thereon, while the ink was wet and tacky. Themodifying powder comprised a commercially obtained petroleum resincomprising a low molecular weight aliphatic hydrocarbon resin derivedmainly from a five carbon diolefin having a Ring and Ball softeningpoint of about 97° to 103° C., a maximum acid number of about 1, asaponification number of less than 2, a bromine number of 45, a densityof 0.97 kg/liter, a flash point of 259° C., and a melt viscosity of 1poise at 230° C., 10 poises at 180° C. and 100 poises at 150° C.(available from Hercules Incorporated, Wilmington, Del. and designatedas "PICCOPALE 100" resin).

The applied powder adhered to the wet ink pattern and the excess powderwas removed from the printed copper surface by means of an air knifehaving pressurized air passing therethrough. The resultant powderdeposited ink patterned surface was then oven heated at 150° C. for 15minutes, fusing the powder to a glossy, continuous coat over the inkpattern. The laminate was then etched as in EXAMPLE I, and then after 14days, immersed in the solvent bath of EXAMPLE I. After one minute at 50°C. in the solvent bath, the composite powder coated oil-modified alkydink pattern was completely removed.

EXAMPLE III

The procedure of EXAMPLE I was repeated except that an ink comprising arosin-modified phenolic resin in treated linseed oil having a viscosityof 2150 to 2350 poises at 25° C. (obtained from Superior Varnish andDrier Company, designated as "No. 3961 Metal Decorating Varnish") wasemployed. The printed surface was oven heated at 150° C. for 10 minutesto dry the ink pattern on the surface. After 14 days, a portion of theink pattern was flooded with methyl chloroform at 25° C. which solventwas permitted to dwell thereon for 20 seconds. The resultant wetted areaof the ink pattern was rubbed with a paper towel in an attempt to removethat portion of the ink pattern. Except for a slight reduction ofsurface gloss the ink pattern was unaffected.

EXAMPLE IV

The procedure of EXAMPLE III was repeated except that after the inkedpattern was printed on the surface the modifying powder of EXAMPLE IIwas applied thereto. After removing excess powder, the resultantpowder-deposited ink pattern surface was then oven heated at 150° C. for10 minutes, fusing the powder to a glossy, continuous coat over the inkpattern. After 14 days, a portion of the coated ink pattern was floodedwith the methyl chloroform as in EXAMPLE III. After 20 seconds theflooded portion of the coated ink pattern was readily and completelywiped off using a paper towel.

It is to be understood that the above-described embodiments are simplyillustrative of the principles of the invention. Various othermodifications and changes may be made by those skilled in the art whichwill embody the principles of the invention and fall within the spiritand scope thereof.

What is claimed is:
 1. A method of rendering an ink, selected from thegroup consisting of an oil-modified alkyd ink and a drying oil vehicleink, strippable from a surface upon which it is applied, dried, andstripped which comprises:(a) applying the ink; (b) prior to the dryingof the applied ink, applying thereto a modifying powder comprising apetroleum resin; (c) fusing said modifying powder which overlies saidink; and (d) stripping the resultant fused coat.
 2. The method asdefined in claim 1 wherein said oil-modified alkyd ink comprises asoybean oil-modified isophthalic pentaerithrytol alkyd.
 3. The method asdefined in claim 2 wherein said modifying powder comprises an aliphaticpolymer resulting predominantly from a five carbon diolefin.
 4. Themethod as defined in claim 1 wherein said drying oil vehicle inkcomprises a linseed oil vehicle.
 5. The method as defined in claim 4wherein said modifying powder comprises an aliphatic polymer resultingpredominantly from a five carbon diolefin.
 6. A method of stripping adried ink pattern from a surface, which comprises:(a) applying an inkpattern comprising an ink selected from the group consisting of anoil-modified alkyd ink and a drying oil ink to the surface of asubstrate; (b) prior to the drying of said ink pattern, dusting thereona modifying powder comprising a petroleum resin to form a powdered inkpattern; (c) heating said powdered ink pattern to fuse at least saiddusted powder to form a modifying coat over the ink pattern; and (d)treating at least said modifying coat covered ink pattern with asuitable solvent to remove said modifying coat covered ink pattern. 7.The method as defined in claim 6 wherein said oil-modified alkyd inkcomprises a soybean oil-modified isophthalic pentaerithrytol alkyd. 8.The method as defined in claim 7 wherein said modifying powder comprisesan aliphatic polymer resulting predominantly from a five carbondiolefin.
 9. The method as defined in claim 6 wherein said drying oilvehicle ink comprises a linseed oil vehicle.
 10. The method as definedin claim 9 wherein said modifying powder comprises an aliphatic polymerresulting predominantly from a five carbon diolefin.
 11. A method ofrendering an ink, selected from the group consisting of an oil-modifiedalkyd ink and a drying oil vehicle ink, wherein said oil-modified alkydink comprises a soybean oil-modified isophthalic pentaerythritol alkydink, strippable from a surface upon which it is applied and dried, whichcomprises:prior to the drying of the applied ink, applying thereto amodifying powder comprising an aliphatic polymer resulting predominantlyfrom a five carbon diolefin.
 12. A method of rendering an ink, selectedfrom the group consisting of an oil-modified alkyd ink and a drying oilvehicle ink, wherein said drying oil vehicle comprises a linseed oilvehicle, strippable from a surface upon which it is applied and dried,which comprises:prior to the drying of the applied ink, applying theretoa modifying powder comprising an aliphatic polymer resultingpredominantly from a five carbon diolefin.